JP5805065B2 - Fasteners made of polymer material - Google Patents

Description

  This application is filed with US Provisional Application No. 61 / 164,599, filed March 30, 2009, and US Provisional Application No. 61 / 164,601, filed March 30, 2009, all of which are incorporated herein by reference. For the purpose of claiming priority benefits based on the above.

  The present invention relates to a fastener made of a specific polyarylene material.

  Many designs of fasteners are available depending on the particular application involved, including nuts, screws, clips, rivets, and many others. These common features lie in the particularly stringent requirements associated with them.

  In practice, all fasteners, including unthreaded and threaded fasteners, are exposed to harsh mechanical conditions and undergo elongation, twisting, and bending during their lifetime. Fasteners are also typically exposed to various corrosive environments such as vibration, thermal cycling, and / or chemical attack, which changes their mechanical performance over time, with worst case assumptions. It is also possible that the fastener will effectively “disappear”.

  A particularly important group of fasteners are threaded fasteners that face other unique problems. When tightening a threaded fastener, we apply energy to it and after release, this energy is held there by frictional constraints. Typically, this frictional constraint is concentrated to a significant degree on the threaded portion of the fastener, and in many cases the threaded portion corresponds to the most fragile portion of the fastener due to its fineness. The corrosive environmental factors described above can cause the threaded fastener to release all of its preload and effectively disappear ("loosening" problem). Somewhat related to loosening is thread collapse, another damage that occurs when a threaded fastener is over-tightened, which is characterized by deformation (changes) in the threaded portion of the fastener, Typically, it causes performance degradation.

  Certain fasteners, including unthreaded and threaded fasteners, can have complex designs, and shaping / machining from the appropriate material can be a daunting problem. In the case of threaded fasteners, it has been found that it is not particularly easy to form fine and regular threaded parts.

  The choice of material is critical to the fastener. Since plastic materials have not been able to provide the required level of mechanical properties, in particular high elongation strength, high bending strength, and finally high torsional strength (or torque) that must not be forgotten, tens of For years, metal was the only preferred option. In practice, in many fasteners, including but not limited to threaded fasteners, the load bearing capacity is typically a function of the shear strength or torsional strength of the constituent materials.

  However, metal fasteners present some drawbacks. Metal fasteners are heavy, but in contrast, certain applications, particularly self-propelled transportation, and more particularly aircraft, require lightweight materials. Metal fasteners are generally prone to corrosion, and in addition, galvanic corrosion can occur when dissimilar metals are joined together. The metal fastener is electrically conductive. Machining complex shapes from metal and the formation of fine and regular threads is a troublesome problem.

  The development of engineering composites such as carbon fiber reinforced polyetheretherketone (PEEK) has successfully provided several practical alternatives for less demanding fastener applications. The addition of fiber reinforcement increases the tensile and bendability well but has little effect on shear. In addition, fiber reinforcement reduces tensile elongation, a measure of practical toughness. In addition, when a fastener is manufactured by an injection molding process using a fiber reinforcement, property variations due to the direction of flow occur. In addition, when the fastener is threaded, the threaded portion is relatively thin and perpendicular to the normal flow direction, so it is unlikely to contain a large amount of fiber reinforcement.

〔式中、ＲおよびＲ’は、−Ｃ（＝Ｏ）Ｃ_６Ｈ_５などの置換基である〕
などで作製された、医療処置のために生体の一部（たとえば頭部）の位置を固定するためのピンが記載されている。 Significant progress was made when the use of rigid rod-like polyphenylene was first proposed for the manufacture of screwless fasteners. Next, EP 20142511 includes optionally substituted polyparaphenylene (first generation non-kink rigid rod-like polyphenylene), for example,

[Wherein R and R ′ are substituents such as —C (═O) C ₆ H ₅ ]
A pin for fixing the position of a part of a living body (for example, the head) for medical treatment is described.

  TECAMAX® SRP polyphenylene, commercially available from Ensinger, is said to be such a material. As a result of their rigid molecular structure, the polyparaphenylenes described in EP 2014251 in fact allow considerably higher torque than conventional composite polymer materials (eg carbon fiber reinforced PEEK). Since reinforcing fibers are not required, uniform materials have significant advantages with respect to uniformity of mechanical properties. However, the first generation of the proposed rigid rod-like polyphenylene has also been proposed in particular by SOLVAY ADVANCED POLYMERS, L.C. However, it is not satisfactory enough to produce the relevant pins. Such polyphenylenes are very demanding as a result of their design (shape, thickness, etc.), especially in certain threadless fasteners, and as a result of the presence of threaded parts in most threaded fasteners. It can be considered “not very satisfactory” in use. In the above highly demanding fastener applications, there remains a need for polymeric materials that provide higher tensile elongation (a measure of practical toughness). Another problem that can be a more serious problem in certain designs than the previous one arises from the inherent stiffness of the first two generations of such proposed polyarylene. That is, it is still difficult to shape them into articles having complex shapes or very thin thicknesses by melt processing techniques such as injection molding or extrusion, as with the original metal.

  Therefore, it exhibits a group of properties including high torque, high practical toughness (high tensile elongation), high elongation strength, high rigidity, high chemical resistance, light weight, and the related parts have complicated shapes and / or Can be easily formed using melt processing techniques such as extrusion or injection molding, including when it has very thin parts (for example, if you have to use an extruder with threads or small orifices), There is an important need for fasteners.

This need and yet another need is for at least one kink in which more than 50 wt% of the repeating units are repeating units (R) represented by one or more formulas consisting of optionally substituted arylene groups. Filled with a fastener (F) comprising a polymeric material (M) comprising a shaped rigid rod-like polyarylene (P). Provided that the optionally substituted arylene group is bonded to two other optionally substituted arylene groups via a direct C-C bond by each of its two ends, The repeating unit (R) is
A rigid rod-forming arylene unit (Ra) optionally substituted with at least one monovalent substituent, from 0 to 75 mol%, based on the total number of moles of repeating units (R);
A kink-forming arylene unit (Rb) optionally substituted with at least one monovalent substituent, from 25 to 100 mol%, based on the total number of moles of the repeating unit (R);
It is a mixture (M) consisting of

Reference will now be made to the accompanying drawings for a detailed description of the invention.
An example of a round bent hook bolt is shown, and A, L, R, C, T, and D are characteristic dimensions of the hook bolt. 2 shows an example of a continuous thread stud according to the present invention. 2 shows an example of a stud bolt according to the present invention. 2 shows an example of a stud bolt according to the present invention. The example of the bushing with an internal and external thread which concerns on this invention is shown. An example of a clevis pin according to the present invention in which a yoke is joined to a rod end is shown. A shows a new cotter pin, B shows a mounted cotter pin, C shows a spring pin, and D shows a cross section (traditional design) of the cotter pin. The example of the taper pin which concerns on this invention is shown. Fig. 3 shows an example of a fastener made of PrimoSpire (R) PR-250 polyphenylene according to the present invention.

Fastener (F)
All terms used herein to describe the fastener (F) are familiar to those skilled in the art and should be understood in their ordinary meaning.

  Fasteners (F) are generally mechanical means specifically designed to hold, join, join, assemble, or balance a single or multiple members. The resulting assembly can function dynamically or statically as a primary or secondary member of the mechanism or structure. Based on the intended application, the fastener (F) can meet varying degrees of built-in accuracy and engineering capabilities and ensure proper and sound use under planned and predetermined environmental conditions.

  The weight of the polymeric material (M) is usually more than 10%, preferably more than 50%, more preferably more than 90%, based on the total weight of the fastener (F). Even more preferably, the fastener (F) consists essentially of the polymeric material (M). Most preferably, the fastener (F) is made of a polymer material (M).

  The fastener (F) can consist of one part. That is, it can be a single member means. In that case, the single part consists of the polymeric material (M). As another option, the fastener (F) may consist of several parts. Depending on the case, a part or some of the fasteners (F) can be made of a polymer material (M). If several parts of the fastener (F) consist of a polymer material (M), each of them can consist of the exact same polymer material (M). As another option, at least two of them can consist of different polymeric materials (M) according to the invention.

  The fastener (F) can be a threaded fastener, ie, a fastener containing a threaded portion.

  The threaded portion is typically a ridge (ie, a raised line or strip) or groove or rib present on at least a portion of the surface of the threaded fastener. The threaded portion may have various forms including a spiral shape, a spiral shape, or a parallel shape. In particular, the threaded portion may exist so as to surround the outer periphery of the specific screw, bolt, and nut.

  Advantageously, at least a part of the thread part contained in the fastener (F) is made of a polymer material (M). Preferably, essentially all the threads contained in the fastener (F) are composed of a polymer material (M). More preferably, all the screw parts contained in the fastener (F) are made of the polymer material (M).

  The threaded surface of the threaded fastener according to the present invention is more than 1% and 2% of the total surface exhibited by the threaded fastener, especially when essentially all of the threaded portion is made of polymer material (M). More than 5%, more than 10%, more than 20%, more than 30%, more than 40%, more than 50%, more than 60%, more than 70%, more than 80%, more than 90%, more than 95%, more than 99%, Or it can occupy about 100%.

  The fastener (F) can be externally threaded. That is, it may have a threaded portion formed on at least a part of a cylindrical or other three-dimensional outer surface, for example, on a bolt or a screw. The thread surface of the externally threaded fastener according to the present invention is more than 1% of the external surface exhibited by the externally threaded fastener, particularly when essentially all of the threaded portion is composed of a polymer material (M). Over 2%, over 5%, over 10%, over 20%, over 30%, over 40%, over 50%, over 60%, over 70%, over 80%, over 90%, over 95%, over 99% Can account for more than or about 100%.

  The fastener (F) can be internally threaded. That is, it may have a threaded portion formed on at least a part of a cylindrical or other three-dimensional inner surface, for example, on a nut. The thread surface of the internally threaded fastener according to the present invention is more than 1% of the interior surface exhibited by the internally threaded fastener, particularly when essentially all of the threaded portion is composed of a polymer material (M). Over 2%, over 5%, over 10%, over 20%, over 30%, over 40%, over 50%, over 60%, over 70%, over 80%, over 90%, over 95%, over 99% Can account for more than or about 100%.

  The fastener (F) can be provided with both internal and external screws. That is, a threaded portion formed on at least a part of a cylindrical or other three-dimensional outer surface, such as an internal / external threaded bushing, and a threaded portion formed on at least a part of the cylindrical or other three-dimensional inner surface, Can be included.

  The present invention is particularly useful when the fastener (F) is a threaded fastener (but not only in this case), where essentially all threads of the threaded fastener are made of polymer material (M). Excellent results are obtained when the thread surface of the threaded fastener occupies more than 10%, preferably more than 20%, more preferably more than 50% of its total surface.

  Common types of threaded fasteners according to the present invention include bolts, nuts, screws, headless screws, scribets, threaded studs, and threaded bushings.

  The fastener (F) can be a bolt. The bolt is typically a headed external threaded fastener. Bolts are generally designed to be inserted into the holes in the assembled part and fit into a nut, and are usually intended to be tightened or released by rotating the nut.

  Certain bolts according to the present invention are considered “bending bolts” in relation to their shape. The bending bolt may in particular be in the form of a “U” bolt, “J” bolt, “L” bolt or eyebolt. “U” shaped bolts typically have threads at both ends, while other listed bending bolts typically have threads at only one end.

Other bolts according to the present invention are as follows.
A square bolt (in relation to the shape of its head being square),
-Hex bolts (in connection with the head shape being hexagonal),
Hexagon flange bolts (similar to hexagonal bolts, but containing a washer-like flat surface that fits into the substrate),
• Round head bolts (typically with round heads at one end, especially those with short square root bolts, round head bolts with ribs, round head bolts with fins, step bolts, countersunk head bolts And slotted countersunk bolts, flat countersunk elevator bolts, T-head bolts, plow bolts, and seam plate bolts).
An eyebolt (typically having a looped head designed to receive a hook or rope, as in the case of the hook bolt illustrated in FIG. 1).

  The fastener (F) can be a nut. A nut is typically an internal thread or intended for use against an external or male thread, such as a bolt, for the purpose of tightening or holding two or more objects in a fixed relative position. It is a perforated block having an internal thread.

  The specific nut according to the present invention is a flange nut. Flange nuts typically have a wide flange at one end that functions as an integrated non-rotating washer, which is usually distributed in the part by distributing the nut pressure over the fixed part. It serves to reduce the possibility of damage and reduce the possibility of loosening as a result of a non-uniform fastening surface. The flange is generally serrated to provide a locking action.

  Another particular nut according to the present invention is a coupling nut. Coupling nuts are typically long nuts that are internally threaded to meet in the middle from each side, not in the same direction throughout, to connect two threaded rods between the ends Can be used.

  Yet another particular nut according to the present invention is a wing nut, also called a knob nut. This is typically a nut with a wing like protrusion for the action of the thumb and index finger levers during rotation.

  The fastener (F) can be a screw. The screw is typically a headed and externally threaded fastener. It usually has the ability to allow the assembled part to be inserted into the hole, the ability to fit into a pre-formed internal screw or form its own thread, and torque the head Has the ability to tighten or release.

  The specific screw according to the present invention is a socket screw. Socket screws are typically screw caps with a hexagonal, splined, or specially shaped hole at the top that requires a matching “screwdriver tip”.

  Another particular screw according to the present invention is a tapping screw. A tapping screw can “thread” an internal screw that fits itself when pushed into pre-formed holes of various materials. The tapping screw is typically a high strength one-piece one-side mounted screwed fastener. Since it can form or cut a threaded part that fits itself, there is an exceptionally good threaded fit that enhances its resistance to loosening in use. The tapping screw according to the present invention is removable and is generally reusable.

  Still another screw according to the present invention is a mechanical screw. A machine screw typically has a thread along the entire length of its shaft. It can also be regarded as a screw with a tapered top that fits into a countersunk hole and contacts the surface to be screwed in when screwed.

  Yet another screw according to the present invention is a thumbscrew or thumbscrew, i.e., a screw that is typically designed to rotate with the thumb and other fingers.

  Still other screws according to the present invention are typically suitable for use in the case of (but not exclusively) a pointed shank, slotted or recessed head, and wood. It is regarded as a “wood screw” in that it has a thread portion with a sharp taper with a relatively coarse pitch.

  Still other screws according to the present invention are considered miniature screws based on their small size. Among the miniature screws, round heads, pan heads, flat heads, and bind heads may be mentioned in particular.

  Screw-washer assemblies (SEMS), at least where the screws comprise polymeric material (M), also form part of the present invention.

  The fastener (F) can be a headless set screw. In contrast to the screw according to the invention defined above which is typically headed, the headless set screw does not have a protruding head. In general, the top is either slotted or provided with a socket.

  The fastener (F) can be a threaded stud. A threaded stud is typically a fastening means in which one pointed end is pushed into a material such as concrete and the other end is threaded and extends over a surface for mounting a structural member It is.

  The particular threaded stud according to the present invention is a continuous threaded stud. That is, it is threaded from end to end and is often used to bolt the flange with two applied nuts. FIG. 2 shows an example of a general purpose continuous thread stud according to the present invention.

  The tip of the continuous thread stud according to the present invention is generally flat and chamfered. The continuous thread stud according to the invention is particularly usable for pipe applications, where it has different length measurement requirements than all other studs, as required for such applications. That is, its length is measured from the first thread to the first thread except for the tip.

  Certain other threaded studs according to the present invention are studs. A typical stud has a short thread at one end called a tap end that is threaded to fit a particular grade (this end is suitable for screwing into a threaded hole. The other end or nut end is threaded with other grades of fitting. The tap end has a chamfered tip, while the nut end can have either a chamfered tip or a rounded tip. FIG. 3 shows an example of a stud bolt according to the present invention.

  Yet another threaded stud according to the invention is a double threaded bolt. Both threaded bolts typically have thread portions of substantially equal or equal length at each end to accommodate the nut and are threaded for a particular grade of fit. Both ends can have a chamfered tip or a rounded tip independent of each other. Both screw bolts are useful for bolting flanges or other applications where torch fusing from both ends is necessary or desirable. FIG. 4 shows an example of a double screw bolt according to the present invention.

  The fastener (F) can be a scribet. A scribet is a threaded fastener that typically includes an at least partially threaded shank and a head. The shank can be threaded on its entire surface. A specific scribet according to the present invention comprises the threaded shank and the head. The scribet is generally inserted into the hole. A scribet is useful for assembling two or more members with an applied force that deforms a flat scribet end to form a finished mechanical joint.

  The fastener (F) can be a threaded bushing. Applicable bushings are internally and / or externally threaded to provide a resistance function in addition to the coupling function. Preferably, it has internal and external screws. An example of a bushing with internal and external threads according to the present invention is a hexagonal bushing shown in FIG.

  In a particular embodiment of the invention, the fastener (F) is a pre-leveling torque type fastener such as a pre-leveling torque type screw or pre-leveling torque type nut. Preveling torque type fasteners can be defined as threaded fasteners that are friction resistant to rotation based on the built-in preveling torque characteristics, and in particular, pre-torque torque type screws are located under the neck of the screw. An externally threaded fastener that is friction resistant to rotation due to the built-in preveling torque characteristics, not due to the compressive load generated on the bearing surface or the tensile load generated on the screw shank; and It can be considered. A specific pre-torque torque type fastener according to the present invention is a fastening made of a polymer material (M) in which an insert of a fusion substance other than the polymer material (M) such as a lubricant is added in the length of a screw portion. It is a tool. Depending on the amount of friction present due to the surface finish and the lubricant, the dimensional characteristics of the insert can be varied to achieve performance requirements.

  The fastener (F) can be a screwless fastener. That is, it does not contain a thread.

  Common types of threadless fasteners according to the present invention include pins, retaining rings, rivets, and fastening washers.

  The fastener (F) can be a pin. The pin is typically a thin, often straight, cylindrical threaded fastener and is suitable for fixing the position of two or more machine parts.

  The specific pin according to the present invention is a clevis pin. A clevis pin is typically a fastener having a head at one end and a hole at the other end that is used to join the clevis to the rod. A clevis is typically a yoke having a hole formed or attached to one end of a rod, and FIG. 6 is an example of a clevis pin according to the present invention that joins the yoke to the rod end. Show. When the eye or hole of the second rod is aligned with the hole in the yoke, it is possible to insert the clevis pin and join them together. The cotter pin can then be inserted into the hole in the clevis pin and retained therein, but nevertheless the fastening can be easily released. This joint is used for rods that are subject to tensile forces that require some flexibility.

  Another particular pin according to the present invention is a cotter pin (US term). A cotter pin is typically a screwless fastener having two tines that can be inserted into a slot for the purpose of holding and integrating the two pieces. A cotter pin traditionally has a semi-circular cross-section. In the UK, the term “divided pin” is traditionally used to describe the same means. The new cotter pin (see FIG. 7A) typically looks like a split cylinder (FIG. 7D) because it has its flat inner surface that contacts most of its length. After insertion, the two ends of the pin are bent away so that it is locked in place (FIG. 7B). To facilitate initial separation of the tines, one tine of the cotter pin is often significantly longer than the other, and the longer tine is often much longer to facilitate insertion into the hole. If it is slightly curved or inclined to overlap the tip of the shorter tine.

  Still another pin according to the present invention is a spring pin. A spring pin (sometimes known as an R pin because of its shape), also called a hitch pin, is also available and is not designed to be permanently bent. . In this design, only one part of the pin passes through the fixed shaft and the other part is curved to surround and cover the outer surface of the shaft (FIG. 7C).

  Still another pin according to the present invention is a tapered pin. A tapered pin is a headless solid pin having a controlled diameter, length, and taper, and generally has a crowned end. This self-holding pin is useful for splicing parts together. Standard taper pins are 1/4 in. ~ 12 in. It has a diaphragm (0.6 cm to 30 cm) and fits by being expanded by being pushed into the drilled hole. It is sometimes used to connect a hub or collar to a shaft. Tapered pins are often used to hold the position of one surface relative to the other. An example of a tapered pin design is shown in FIG.

  Still another pin according to the present invention is a dowel pin. In many cases, dowel pins typically have sharpened or deformed ends. It can be inserted into the holes of two adjacent pieces to hold them together. It is particularly useful for fastening tenon joints. Dowel pins can be obtained by cutting dowel rods or solid cylindrical rods into short lengths.

  Still another pin according to the present invention is a parallel pin. Parallel pins typically have an unground straight cylindrical surface that is chamfered at both ends.

  Yet another pin according to the present invention is a grooved pin. A grooved pin is a pin with a groove, and the grooved pin often has three grooves that are equally spaced on the diameter of the pin.

  The fastener (F) can be a retaining ring. The retaining ring is typically a flat circular unthreaded fastener with a hollow center and an open cross-section. The retaining ring typically provides a shoulder and can be inserted on the shaft or inside a hole with an internal groove.

  The fastener (F) can be a rivet. A rivet is typically a screwless fastener including a shank and a head, and a particular rivet according to the present invention consists of the shank and the head. The rivet is generally inserted into the hole. The rivet shank can be formed in the shape of an alignment head located on the other side of the rivet. A rivet is useful for assembling two or more members with an applied force that deforms a flat rivet end to form a finished mechanical joint.

  The fastener (F) can be a fastening washer such as a lock washer. A lock washer is typically a washer placed under a nut or screw for the purpose of preventing loosening by applying pressure. The lock washer according to the invention advantageously has a helical structure that serves to apply pressure. Spring washers are similar to lock washers.

Kink type rigid rod-shaped polyarylene (P)
For the purposes of the present invention, an arylene group is a single benzene ring or a single nucleus composed of a plurality of benzene rings fused together by sharing two or more adjacent ring carbon atoms. And a hydrocarbon divalent group having two ends.

Examples of arylene groups include, but are not limited to, phenylene, naphthylene, anthrylene, phenanthrylene, tetrasenylene, triphenylylene, pyrenylene, and peryleneylene. Arylene groups (especially the numbering of the ring carbon atoms) were named in compliance with ^{CRC Handbook of Chemistry and Physics, 64} th C1-C44 pages and recommended standard of country C11-C12 page of edition.

  Arylene groups usually exhibit a certain level of aromaticity. For this reason, it is often reported as an “aromatic” group. The level of aromaticity of the arylene group depends on the nature of the arylene group and is described in Chem. Rev. 2003, 103, 3449-3605, “Aromaticity of Polycyclic Conjugated Hydrocarbons”, the level of aromaticity of polycyclic aromatic hydrocarbons is specifically defined on page 3531 of the same paper. The value of B for a group of many polycyclic aromatic hydrocarbons is reported in Table 40 on the same page.

  The terminal of the arylene group is a free electron of a carbon atom contained in the benzene ring of the arylene group, and a hydrogen atom bonded to the carbon atom is removed. Each end of the arylene group can form a bond with another chemical group. The end of the arylene group, more precisely the bond that can be formed by the end, can be characterized by the direction and orientation, and for the purposes of the present invention the orientation of the end of the arylene group is from the inside of the core of the arylene group. Defined as going outside the nucleus. More precisely, for arylene groups whose ends have the same direction, such ends can be either in the same orientation or in the opposite orientation. Also, their ends may be in line with each other or not (in other words, they may not cross each other).

Polyarylene shall mean a polymer in which more than 50 wt% of the repeating units are repeating units (R) represented by one or more formulas consisting of optionally substituted arylene groups. However, the optionally substituted arylene group is bonded to the two other optionally substituted arylene groups via a direct C-C bond by each of its two ends. Yes. That an optionally substituted arylene group is bonded to each of its two ends by a direct C-C bond to two other optionally substituted arylene groups. , An essential feature of the repeating unit (R). Thus, as follows:
_{-O-φ 1 -S (= O} ) 2 -,
-O-φ ₂ -φ _{2 '} -O-,
When the arylene repeating unit is bonded to a group other than an arylene group such as phenylene repeating unit φ ₁ , φ ₂ , and φ _{2 ′} by at least one of its two ends, the present invention Is not a repeat unit (R).

  The arylene group constituting the repeating unit (R) may be unsubstituted. As another option, they can be substituted with at least one monovalent substituent.

  Monovalent substituents are usually not essentially macromolecules, and their molecular weight is preferably less than 500, more preferably less than 300, even more preferably less than 200, and most preferably less than 150.

  The monovalent substituent is advantageously a solubilizing group. Solubilizing groups are at least one organic solvent that can be used as a solvent during the synthesis of polyarylene by a solution polymerization process, in particular dimethylformamide, N-methylpyrrolidinone, hexamethylphosphoric triamide, benzene, tetrahydrofuran, and dimethoxyethane. A group that increases the solubility of the polyarylene in at least one of the above.

  Monovalent substituents are also advantageously groups that increase the fusibility of the polyarylene. That is, it lowers its glass transition temperature and its melt viscosity, preferably in order to make the polyarylene suitable for thermal processing.

Preferably, the monovalent substituent is selected from:
Hydrocarbyl, such as alkyl, aryl, alkylaryl, and aralkyl, etc.
Halogeno, such as -Cl, -Br, -F, and -I, etc.
Hydrocarbyl groups partially or fully substituted by at least one halogen atom, such as halogenoalkyl, halogenoaryl, halogenoalkylaryl, and halogenoaralkyl, etc.
Hydroxyl,
Hydrocarbyl groups substituted by at least one hydroxyl group, such as hydroxyalkyl, hydroxyaryl, hydroxyalkylaryl, and hydroxyaralkyl, etc.
Hydrocarbyloxy [—O—R wherein R is a hydrocarbyl group]], for example, alkoxy, aryloxy, alkylaryloxy, aralkyloxy, etc.
Amino _(-NH 2),
A hydrocarbyl group substituted by at least one amino group, such as aminoalkyl and aminoaryl,
Hydrocarbylamine [—NHR or —NR ₂ wherein R is a hydrocarbyl group]], such as alkylamines and arylamines, etc.
Carboxylic acids and their metal or ammonium salts, carboxylic acid halides, carboxylic acid anhydrides,
A hydrocarbyl group substituted by at least one of a carboxylic acid, its metal salt or ammonium salt, a carboxylic acid halide, and a carboxylic anhydride, eg, —R—C (═O) OH, wherein R is alkyl Group or aryl group), etc.
Hydrocarbyl esters [—C (═O) OR or —O—C (═O) R wherein R is a hydrocarbyl group]], for example, alkyl esters, aryl esters, alkylaryl esters, aralkyl esters, and the like ,
An amide [—C (═O) NH ₂ ],
A hydrocarbyl group substituted by at least one amide group,
Hydrocarbyl amide monoesters [—C (═O) NHR or —NH—C (═O) —R where R is a hydrocarbyl group]], for example, alkylamides, arylamides, alkylarylamides, and Aralkylamides and the like, as well as hydrocarbylamide diesters [—C (═O) NR ₂ or —N—C (═O) R _{2 wherein} R is a hydrocarbyl group]], for example, dialkylamides and diarylamides,
Sulfinic acid (—SO ₂ H), sulfonic acid (—SO ₃ H), their metal salts or ammonium salts,
Hydrocarbyl sulfone [—S (═O) ₂ —R wherein R is a hydrocarbyl group]], for example, alkyl sulfone, aryl sulfone, alkylaryl sulfone, aralkyl sulfone, etc.
An aldehyde [—C (═O) H] and a haloformyl [—C (═O) X wherein X is a halogen atom]],
Hydrocarbyl ketones [—C (═O) —R wherein R is a hydrocarbyl group]], such as alkyl ketones, aryl ketones, alkyl aryl ketones, and aralkyl ketones, etc.
A hydrocarbyloxyhydrocarbyl ketone [—C (═O) —R ¹ —O—R ^{2 wherein} R ¹ is a divalent hydrocarbon group such as alkylene, arylene, alkylarylene, or aralkylene, preferably C ₁ -C ₁₈ alkylene, phenylene, and the like at least one of a phenylene group substituted by an alkyl group or at least one alkylene group substituted by a phenyl group, and R ² is a hydrocarbyl group, for example, an alkyl group, Aryl groups, alkylaryl groups, aralkyl groups, etc.]], for example, alkyloxyalkyl ketones, alkyloxyaryl ketones, alkyloxyalkylaryl ketones, alkyloxyaralkyl ketones, aryloxyalkyl ketones, aryloxy aryls Ruketone, aryloxyalkyl aryl ketone, and aryloxy aralkyl ketone,
Any one of the foregoing groups comprising at least one hydrocarbyl group or divalent hydrocarbon group R ¹ , wherein said hydrocarbyl group or said R ¹ itself is at least one of the monovalent substituents listed above Substituted) by, for example, aryl ketone-C (= O) -R, wherein R is an aryl group substituted by one hydroxyl group;
here,
The hydrocarbyl group preferably contains 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, even more preferably 1 to 6 carbon atoms,
The alkyl group preferably contains 1 to 18 carbon atoms, more preferably 1 to 6 carbon atoms, very preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, And tert-butyl,
An aryl group is composed of one end and one benzene ring (for example, a phenyl group) or a plurality of benzene rings (for example, a biphenyl group) directly connected to each other via a carbon-carbon bond, or two or more Defined as a monovalent group consisting of one nucleus composed of a plurality of benzene rings fused together by sharing adjacent ring carbon atoms (for example, a naphthyl group, etc.), provided that the ring carbon atom is Can be replaced by at least one nitrogen, oxygen, or sulfur atom, and preferably in the aryl group, the ring carbon atom is not replaced;
The aryl group preferably contains 6 to 30 carbon atoms, more preferably a phenyl group,
・ The alkyl group contained in the alkylaryl group satisfies the above-mentioned preference of the alkyl group,
-The aryl group contained in the aralkyl group satisfies the above-mentioned priority of the aryl group.

More preferably, the monovalent substituent is hydrocarbyl ketone [—C (═O) —R wherein R is a hydrocarbyl group]] and hydrocarbyloxyhydrocarbyl ketone [—C (═O) —R ¹ —O. -R ^{2 wherein} R ¹ is a divalent hydrocarbon group and R ² is a hydrocarbyl group, and the hydrocarbyl ketone and the hydrocarbyloxyhydrocarbyl ketone are unsubstituted or Substitution with at least one of the monovalent substituents listed above.

  Even more preferably, the monovalent substituent is selected from aryl ketones and aryloxy aryl ketones, said aryl ketone and aryloxy aryl ketone being unsubstituted or at least of the monovalent substituents listed above. Is replaced by one.

  Most preferably, the monovalent substituent is an (unsubstituted) aryl ketone, specifically phenyl ketone [—C (═O) -phenyl].

  The nucleus of the optionally substituted arylene group in the repeating unit (R) is preferably composed of at most 3, more preferably at most 2 and even more preferably at most 1 benzene ring. . In that case, when the nucleus of the arylene group which may be optionally substituted in the case of the repeating unit (R) is composed of one benzene ring, the repeating unit (R) may be an optionally substituted phenylene group. Wherein the optionally substituted phenylene group is substituted by each of its two ends by two other optionally substituted via a direct C—C bond. To an arylene group which may be substituted.

  As explained above, the arylene group which may optionally be substituted in the repeating unit (R) is substituted by two other cases via a direct C—C bond with each of its two ends. To an arylene group which may be present. Preferably it is linked by two of its two ends to two other optionally substituted phenylene groups via a direct C-C bond.

  Similarly, as explained above, both ends of the arylene group which may optionally be substituted in the repeating unit (R) can be characterized in particular by direction and orientation.

The first set of repeating units (R) is composed of an optionally substituted arylene group, the ends of which are
Have the same direction,
-Opposite orientations; and-in line with each other [from now on, rigid rod-forming arylene units] (Ra).

Examples of optionally substituted arylene groups include the following, and those substituted with at least one monovalent substituent as defined above, specifically with a phenyl ketone group: Any of these groups may be mentioned, but the invention is not limited to these.

  The optionally substituted p-phenylene is advantageous as a rigid rod-forming arylene unit (Ra).

  Rigid rod-forming arylene units (Ra), when contained in polyarylene, produce linear polymer chains that exhibit excellent stiffness. For this reason, such polyarylenes are generally referred to as “rigid rod polymers”.

The second set of repeating units (R) is composed of optionally substituted arylene groups, the ends of which are
Either have different directions to form an angle of 0 to 180 ° with each other (the angle can be acute or obtuse);
Or have the same direction and the same direction,
Or they have the same direction and are in opposite directions and do not cross each other (ie are not in line with each other)
[Generally referred to hereinafter as the kink-forming arylene unit (Rb)].

In this case, the first subset of kink-forming arylene units (Rb) is composed of optionally substituted arylene groups whose ends have different directions and form acute angles with each other [ Kink-forming arylene unit] (Rb-1). Examples of optionally substituted arylene groups in which the ends have different directions from each other include the following, and at least one monovalent substituent as defined above, specifically a phenyl ketone group. Although any of these substituted groups is mentioned, it is not limited to these.

The second subset of kink-forming arylene units (Rb) is made up of optionally substituted arylene groups, the ends of which have different directions and form obtuse angles with each other [kink-forming units ] (Rb-2). Examples of optionally substituted arylene groups in which the ends have different directions from each other include the following, and at least one monovalent substituent as defined above, specifically a phenyl ketone group. Although any of these substituted groups is mentioned, it is not limited to these.

The third subset of the kink-forming arylene unit (Rb) is composed of an optionally substituted arylene group, and the terminal has the same direction and the same direction [kink-forming arylene unit] (Rb-3). Examples of arylene groups which may be optionally substituted if the ends are in the same direction and in the same direction are, in particular, by the following and at least one monovalent substituent as defined above: Any of these groups substituted by a phenylketone group can be mentioned, but not limited thereto.

好ましくは、キンク形成性アリーレンユニット（Ｒｂ）は、キンク形成性アリーレンユニット（Ｒｂ−１）、キンク形成性アリーレンユニット（Ｒｂ−２）、およびキンク形成性アリーレンユニット（Ｒｂ−４）から選択される。より好ましくは、キンク形成性アリーレンユニット（Ｒｂ）は、キンク形成性アリーレンユニット（Ｒｂ−１）およびキンク形成性アリーレンユニット（Ｒｂ−２）から選択される。さらにより好ましくは、キンク形成性アリーレンユニット（Ｒｂ）は、キンク形成性アリーレンユニット（Ｒｂ−１）から選択される。そのうえさらにより好ましくは、キンク形成性アリーレンユニット（Ｒｂ）は、場合により置換されていてもよいｍ−フェニレンである。 The fourth subset of kink-forming arylene units (Rb) is composed of optionally substituted arylene groups, the ends of which are in the same direction and in opposite directions, and [Kink-forming arylene unit] (Rb-4) not intersected. Examples of optionally substituted arylene groups include the following, and those substituted with at least one monovalent substituent as defined above, specifically with a phenyl ketone group: Any of these groups may be mentioned, but the invention is not limited to these.

Preferably, the kink-forming arylene unit (Rb) is selected from the kink-forming arylene unit (Rb-1), the kink-forming arylene unit (Rb-2), and the kink-forming arylene unit (Rb-4). . More preferably, the kink-forming arylene unit (Rb) is selected from a kink-forming arylene unit (Rb-1) and a kink-forming arylene unit (Rb-2). Even more preferably, the kink-forming arylene unit (Rb) is selected from the kink-forming arylene unit (Rb-1). Even more preferably, the kink-forming arylene unit (Rb) is an optionally substituted m-phenylene.

  The kink-forming arylene unit (Rb), when contained in polyarylene, produces more or less kink-shaped polymer chains and exhibits higher solubility and fusibility than linear polymer chains. For this reason, such polyarylenes are generally referred to as “kink-type polymers”.

The repeating unit (R) of the kink-shaped rigid rod-like polyarylene (P) must be of a specific type. That is,
A rigid rod-forming arylene unit (Ra) optionally substituted with at least one monovalent substituent, from 0 to 75 mol%, based on the total number of moles of repeating units (R);
A kink-forming arylene which may be optionally substituted by at least one monovalent substituent, in an amount of 25 to 100 mol%, based on the total number of moles of repeating units (R) A unit (Rb);
It must be a mixture (M).
The repeating unit (R) is preferably
A rigid rod-forming arylene unit (Ra) selected from 0-75 mol%, optionally substituted p-phenylene, based on the total number of moles of repeating units (R);
25 to 100 mol%, based on the total number of moles of repeating units (R), (i) optionally substituted m-phenylene and (ii) optionally substituted m-phenylene And a kink-forming arylene unit (Rb) selected from a mixture of optionally substituted o-phenylene,
It is a mixture (M) consisting of

Preferably, essentially, if not all, of the rigid rod-forming arylene units (Ra) in the mixture (M) are p-phenylene units substituted with at least one substituent. More preferably, essentially all if not all rigid rod-forming arylene units (Ra) in mixture (M) are hydrocarbyl ketone [—C (═O) —R, where R is Is a hydrocarbyl group]] and hydrocarbyloxyhydrocarbyl ketone [—C (═O) —R ¹ —O—R ^{2 wherein} R ¹ is a divalent hydrocarbon group and R ² is a hydrocarbyl group] P-phenylene substituted with at least one monovalent substituent selected from However, the hydrocarbyl ketone and the hydrocarbyloxyhydrocarbyl ketone are themselves unsubstituted or substituted with at least one monovalent substituent as listed above. Even more preferably, essentially all if not all rigid rod-forming arylene units (Ra) in mixture (M) are at least one selected from aryl ketones and aryloxy aryl ketones. P-phenylene substituted by a valent substituent. However, the aryl ketone and the aryloxy aryl ketone are unsubstituted or substituted with at least one monovalent substituent as listed above. Most preferably essentially all if not all rigid rod-forming arylene units (Ra) in the mixture (M) are substituted by arylketone groups, in particular by phenylketone groups. -Phenylene.

Essentially all if not all kink-forming arylene units (Rb) in the mixture (M) are m-phenylene units optionally substituted by at least one substituent. More preferably, essentially all if not all kink-forming arylene units (Rb) in the mixture (M) are hydrocarbyl ketone [—C (═O) —R, wherein R is a hydrocarbyl group. ]] And hydrocarbyloxyhydrocarbyl ketone [—C (═O) —R ¹ —O—R ^{2 wherein} R ¹ is a divalent hydrocarbon group and R ² is a hydrocarbyl group]]. M-phenylene units optionally substituted by at least one selected monovalent substituent. However, the hydrocarbyl ketone and the hydrocarbyloxyhydrocarbyl ketone are themselves unsubstituted or substituted with at least one monovalent substituent as listed above. Even more preferably essentially all if not all kink-forming arylene units (Rb) in the mixture (M) are unsubstituted m-phenylene units.

  In the mixture (M), the number of moles of kink-forming arylene units (Rb) is preferably at least 25%, more preferably at least 30%, even more preferably based on the total number of moles of repeating units (R). At least 35%, even more preferably at least 40%, most preferably at least 45%. On the other hand, the number of moles of the kink-forming arylene unit (Rb) in the mixture (M) is preferably at most 90%, more preferably at most 75%, based on the total number of moles of the repeating unit (R). Even more preferably at most 65%, most preferably at most 55%.

  Good results have been obtained when the repeating unit (R) is a mixture of p-phenylene units substituted with phenylketone groups and unsubstituted m-phenylene units in a molar ratio of about 50:50. .

The kink-shaped rigid rod-shaped polyarylene (P) may further include a repeating unit (R ^* ) different from the repeating unit (R).

The repeating unit (R ^* ) may or may not contain at least one strong divalent electron withdrawing group bonded to the arylene group at each of its ends. Examples of repeating units (R ^* ) that do not contain such strong divalent electron withdrawing groups include, but are not limited to:

で示される反復ユニット
（ｉｉ） 式

で示される反復ユニット
〔式中、Ｑは、

｛ここで、ｎは１〜６の整数であり、かつｎ’は２〜６の整数である｝
から選択される基であり、Ｑは、好ましくは、

から選択される〕
（ｉｉｉ） 式

で示される反復ユニット
（ｉｖ） 式

で示される反復ユニット The repeating unit (R ^* ) preferably contains at least one strong divalent electron withdrawing group bonded to an arylene group, in particular a p-phenylene group, at each of its ends. The divalent electron withdrawing group is preferably a sulfone group [—S (═O) ₂ —], a carbonyl group [—C (═O) —], a vinylene group [—CH═CH—], a sulfoxide group [ —S (═O) —], azo group [—N═N—], saturated fluorocarbon group such as —C (CF ₃ ) ₂ —, organic phosphine oxide group [—P (═O) (═R _h ) - wherein, _{R h} is a hydrocarbyl group]], and ethylidene group [-C (= CA ₂₎ - in the formulas, a may be hydrogen or halogen]. More preferably, the divalent electron withdrawing group is selected from a sulfone group and a carbonyl group. Even more preferably, the repeating unit (R ^* ) is selected from:
(I) Formula

Iteration unit represented by (ii)

(Where Q is

{Where n is an integer from 1 to 6 and n ′ is an integer from 2 to 6}
Q is preferably a group selected from

Selected from)
(Iii) Formula

Repeat unit (iv) expressed by

Iteration unit indicated by

  Preferably more than 75 wt%, more preferably more than 90 wt% of the repeat units in the polyarylene are repeat units (R). Even more preferably, essentially all, if not all, repeat units in the polyarylene are repeat units (R).

  The polyarylene is a kink-shaped rigid rod-like polyphenylene in which essentially all if not all repeating units are 10:90 to 70:30, preferably 25:75 to 65:35, more preferably P-phenylene substituted with a phenyl ketone group in a molar ratio p-phenylene: m-phenylene of 35: 65-60: 40, even more preferably 45: 55-55: 45, most preferably about 50:50 In the case of a mixture with unsubstituted m-phenylene, excellent results were obtained. Such a kink-shaped rigid rod-like polyphenylene is disclosed in Solvay Advanced Polymers, L. as PrimoSpire® PR-250 polyphenylene. L. C. Commercially available.

  The kink-shaped rigid rod-like polyarylene (P) usually has a number average molecular weight of greater than 1000, preferably greater than 5000, more preferably greater than about 10,000, and even more preferably greater than 15,000. On the other hand, the number average molecular weight of the kink-shaped rigid rod-shaped polyarylene is usually less than 100,000, preferably less than 70000. In certain embodiments, the number average molecular weight of the kink-shaped rigid rod-shaped polyarylene is greater than 35000. In other embodiments, it is at most 35000, and in this embodiment it is often at most 25000 and sometimes at most 20000. The number average molecular weight of common polyarylenes, in particular those of kink-shaped rigid rod-like polyarylenes (P), are advantageously (1) “relative” of polyarylenes by gel permeation chromatography (GPC) using polystyrene calibration standards. The number average molecular weight is measured, and then (2) the “relative” number average molecular weight so measured is divided by two. Those skilled in the art who are specialists in polyarylene know that their “relative” number average molecular weight, as measured by GPC, generally deviates by a factor of two and are treated accordingly. This correction factor is taken into consideration for both the lower limit and the upper limit of the molecular weight mentioned above.

  It can be amorphous (ie, has no melting point) or semi-crystalline (ie, has a melting point). It is preferably amorphous.

  It advantageously has a glass transition temperature above 50 ° C, preferably above 120 ° C, more preferably above 150 ° C.

〔式中、Ａｒｙは多価アリーレンであり、かつｘは、２を超える結合数ｘ≧１を表す〕
を本質的に含まないかまたはまったく含まない。 The kink-shaped rigid rod-like polyarylene (P) is generally unbranched. In particular, it is generally a repetitive branching unit

[In the formula, Ary is a polyvalent arylene, and x represents the number of bonds x ≧ 1 exceeding 2.]
Is essentially free of or not at all.

  The kink-shaped rigid rod-like polyarylene (P) can be prepared by any method. Methods well known in the art for preparing such kink-shaped rigid rod-like polyarylenes are: (i) optionally substituted rigid rod-forming arylene groups (at their two ends, chlorine, At least one dihaloarylene molecular compound consisting of bromine and one halogen atom such as iodine) (ii) an optionally substituted kink-forming arylene group (the two Polymerizing with at least one dihaloarylene molecular compound consisting of chlorine, bromine, iodine, and fluorine at each end, which is bonded to one halogen atom, such as chlorine, preferably by reductive coupling. including. When the halogen atom is eliminated from the dihaloarylene molecular compound, an optionally substituted rigid rod-forming arylene group and an optionally substituted kink-forming arylene group are obtained, respectively.

Thus, for example:
When both chlorine atoms are desorbed from p-dichlorobenzene, p-dichlorobiphenyl, or their homologous molecules represented by the general formula Cl- (φ) _N —Cl, where N is an integer of 3-10, 1, 2, or N adjacent p-phenylene units (rigid rod-forming arylene units) are formed, respectively, so that p-dichlorobenzene, p-dichlorobiphenyl, and the general formula Cl- ( Those homologues represented by [phi]) N-Cl are polymerizable to form p-phenylene units.
2,5-dichlorobenzophenone (p-dichlorobenzophenone) can be polymerized to form 1,4- (benzoylphenylene) units (also rigid rod-forming arylene units).
M-Dichlorobenzene can be polymerized to form m-phenylene units (kink-forming arylene units).

  In the present invention, 1, 2, 3, or even more than three different kink-shaped rigid rod-like polyarylenes (P) can be used.

The polymer material (M) described above in the components that may optionally be present may further include one or more polymers and / or one or more non-polymeric additives other than the kink-shaped rigid rod-shaped polyarylene (P) ( (Collectively referred to as components that may optionally be present).

Related non-polymeric additives include, among others, fibrous reinforcing agents, particulate fillers and nucleating agents such as talc and silica, adhesion promoters, compatibilizers, curing agents, lubricants, metal particles, mold release agents, TiO ₂ and organic pigments such as carbon black and / or inorganic pigments, dyes, flame retardants, smoke suppressants, heat stabilizers, antioxidants, UV absorbers, tougheners such as rubber, plasticizers, antistatic agents , Melt viscosity reducing agents, and mixtures thereof.

In a first particular embodiment, the polymeric material (M) further comprises at least one polyarylene other than the kink-shaped rigid rod-like polyarylene (P). The polyarylenes other than the kink-shaped rigid rod-like polyarylene (P) are preferably a repeating unit (R2) represented by one or more formulas in which more than 50 wt% of the repeating units consist of an optionally substituted arylene group. ), A kink-shaped rigid rod-shaped polyarylene (P2). However, the optionally substituted arylene group is bonded to the two other optionally substituted arylene groups via a direct C-C bond by each of its two ends. And the repeating unit (R2) is
A rigid rod-forming arylene unit (R2a) optionally substituted by at least one monovalent substituent, from 75 mol% to 100 mol%, based on the total number of moles of the repeating unit (R2) When,
-0 to 25 mol% of the kink-forming arylene unit (R2b) optionally substituted by at least one monovalent substituent, based on the total number of moles of the repeating unit (R2);
(M2).

  Unless otherwise stated, the kink-shaped rigid rod polyarylene (P2) advantageously satisfies all the properties of the kink-shaped rigid rod polyarylene (P) detailed above at any priority level.

  The amount of the repeating unit (R2a) and (R2b) of the kink-shaped rigid rod-shaped polyarylene (P2), the number of moles of the kink-forming arylene unit (R2b) in the mixture (M2) is the total number of moles of the repeating unit (R2). Is preferably at least 1.0%, more preferably at least 5%, even more preferably at least 10%. On the other hand, in the mixture (M2), the number of moles of the kink-forming arylene unit (R2b) is preferably at most 20%, more preferably at most 18%, based on the total number of moles of the repeating unit (R2). . The polyarylene (P2) is a kink-shaped rigid rod-like polyphenylene copolymer, and essentially all if not all of the repeating units are 80:20 to 95: 5, preferably 80:20 to 90:10. Even more preferably, it is a mixture (M2) of p-phenylene: m-phenylene having a molar ratio of about 85:15 and p-phenylene substituted with a phenylketone group and unsubstituted m-phenylene (M2). Results. Such a kink-shaped rigid rod-shaped polyphenylene copolymer is disclosed in Solvay Advanced Polymers, L. as PrimoSpire® PR-120 polyphenylene. L. C. Commercially available.

  In this first particular embodiment, the weight of polyarylene (P2) is at least 1%, at least 5%, at least 10%, or at least 15%, based on the total weight of the polymeric material (M) sell. On the other hand, the weight of polyarylene (P2) can be at most 99%, at most 95%, at most 75%, at most 60%, based on the total weight of the material.

  In other specific embodiments, the polymeric material (M) further comprises a polyamide (eg, polyphthalamide), a polyether block amide, a polyimide, a polyetherimide, a polyamideimide, a polyarylethersulfone (eg, polyphenylsulfone, Bisphenol A polysulfone, polyethersulfone, polyetherethersulfone, etc., polyethersulfonimide, and copolymers and mixtures thereof), polyetherketone, polyetheretherketone, polyetherketoneketone, polyarylene ether [eg, polyphenylene ether And poly (2,6-dimethyl-1,4-phenylene ether)], polyphenylene sulfide, polybenzimidazole, polycarbonate, polyester At least one other than polyarylene selected from the group consisting of polyethylene, polyurethane, polyolefin, poly (methylpentene), polytetrafluoroethylene, polyethylene, polypropylene, liquid crystal polymer, halogenated polymer, and copolymers and mixtures thereof. Includes thermoplastic polymers.

  In yet another particular embodiment, the polymeric material (M) further comprises at least one fibrous reinforcing agent, in particular an inorganic fibrous reinforcing agent such as glass fiber or carbon fiber, usually a polymeric material (M ) In an amount of 10 to 50% by weight based on the total weight.

  In a preferred embodiment, the polymeric material (M) is essentially free of any fibrous reinforcing agent, especially inorganic fibrous reinforcing agents such as glass fibers and carbon fibers. More preferably, it does not contain any fibrous reinforcing agent.

  In other preferred embodiments, the polymeric material (M) contains 0-1% metal, more preferably 0-0.1% metal. Even more preferably, it is essentially free of any metal, most preferably free of any metal.

  The weight of components which may optionally be present, based on the total weight of the material, is advantageously 0-75% by weight, preferably 0-50% by weight, based on the total weight of the polymer material (M) More preferably, it is in the range of 0 to 25% by weight, even more preferably 0 to 10% by weight, and even more preferably 0 to 5% by weight. Excellent results are obtained when the material is essentially free or completely free of components that may be present in the foregoing cases.

  Fastener (F) can be used as it is or ball lock pin, latch, clip, clip nut, plug and sleeve, floating nut fastener, isolator mount, nut plate, split joint fixture, floor fixture, quarter turn Used as a component of many means such as fasteners, inserts, support brackets, mount bracket mounts, latches, release pins, hinges, bolt bushings, cable ties, tubing hangers, wiring clamps, standoffs, spacers, conduit brackets, etc. Is possible.

  The fastener (F) is particularly useful for demanding applications. For example, it is particularly suitable for aircraft and other self-propelled transportation applications where lightness, torque, strength, toughness, and thermal degradability are important properties.

  Accordingly, another aspect of the invention relates to an aircraft comprising at least one fastener (F) as described above.

  Fasteners (F) include, in particular, aircraft partitions, aircraft sidewalls, aircraft floors, aircraft ceiling panels, aircraft passenger transport units, aircraft fitting panels, aircraft lighting sidewalls and ceilings, aircraft video monitors, aircraft luggage compartments, aircraft Oxygen boxes, aircraft HVAC duct systems, aircraft food trays, aircraft armrests, aircraft seat structures, aircraft toilets, cooking rooms, and barrow sidebars, aircraft cockpit instruments, aircraft wire and cable harnesses and clamps And can be incorporated into aircraft power generation and distribution systems.

The following are mentioned as a related aspect of this invention.
The use of an aircraft comprising at least one fastener (F) as described above for boarding passengers and / or loading luggage;
The use of an aircraft comprising at least one fastener (F) as described above for the transport of passengers and / or luggage;
The use of an aircraft comprising at least one fastener (F) as described above for the unloading of passengers and / or the unloading of luggage from said aircraft;
Non-aircraft air transport (the air transport includes at least one fastener (F) as described above), in particular helicopters, hot air balloons, gliders, and space rockets and space shuttles,
A self-propelled transport other than an air transport (the self-propelled transport includes at least one fastener (F) as described above), in particular an automobile, motorcycle, truck or van,
A self-propelled transport comprising at least one fastener (F) as described above,
The use of a self-propelled transport including at least one fastener (F) for the transport of passengers and / or luggage;

  More generally, the fastener (F) will be useful in any industrial application where chemical resistance, mechanical resistance, light weight, corrosion resistance, and / or electrical insulation are important, such as the semiconductor industry. . Accordingly, yet another aspect of the present invention relates to the use of fasteners (F) in semiconductor applications.

Set 1
PrimoSpire® PR-250 polyphenylene (the latest generation of high kink rigid rod-shaped polyarylene commercially available from SOLVAY ADVANCED POLYMERS, L.C.) and both unreinforced and carbon fiber reinforced PEEK The physical and mechanical properties of are shown in Table 1. As can be seen from the following results, it is essentially impossible to predict fastener performance from the nature of the data sheet.

  Several tests were conducted to demonstrate the usefulness of PrimoSpire® PR-250 polyphenylene as a material suitable for fasteners, particularly aerospace fasteners. Fastener tests included failure torque and tensile strength. Both inner and outer screws were evaluated.

In order to evaluate the internal thread in the screw, the hole provided by drilling the specimen of the test material. The holes were then threaded using appropriate taps. A steel machine screw was attached and the damage torque was measured. In this test, the thread part was damaged when the thread crushed. The test results shown in Table 2 show that PrimoSpire® PR-250 is clearly superior to 30% carbon fiber reinforced PEEK. The unreinforced PEEK data also shows that the torque strength was not substantially improved by the addition of 30% carbon fiber.

Accordingly, yet another aspect of the present invention is that at least one of the repeating units (R) represented by one or more formulas, wherein more than 50 wt% of the repeating units consist of optionally substituted arylene groups. To the use of kink-shaped rigid rod-shaped polyarylene (P). However, the optionally substituted arylene group is bonded to the two other optionally substituted arylene groups via a direct C-C bond by each of its two ends. And the repeating unit (R) is
A rigid rod-forming arylene unit (Ra) optionally substituted with at least one monovalent substituent, from 0 to 75 mol%, based on the total number of moles of repeating units (R);
At least one to increase the torque of the polymer material (M) suitable for the production of the fastener (F) as described above, based on the total number of moles of the repeating unit (R), 25-100 mol% A kink-forming arylene unit (Rb) optionally substituted by a monovalent substituent of
It is a mixture (M) consisting of

To test the external screw external screw, a mechanical screw was injection molded from the candidate resin. A hole was drilled in a 0.625 "(16 mm) thick steel plate. The hole was threaded using a suitable tap. The screw to be tested was attached and then torque was applied until the screw broke. Torque values are shown in Table 3. The torque required to break the PrimoSpire® PR-250 screw is approximately twice that required to break the 30% CF PEEK screw.

Tensile strength data Tensile strength data was obtained using the NASM 1312-8A test method and 10-32 machined injection molded screws. The results are shown in Table 4. SRP showed higher tensile strength and much smaller standard deviation than 30% carbon fiber reinforced PEEK.

Other Important Considerations Although this experimental data was obtained with machine screws, the conclusions apply to many fasteners such as bolts, nuts, washers, pins, and scribets. Engineering fasteners such as clip nuts, nut plates, mounts, inserts, latches, hinges, clamps, and spacers should also be considered candidates for weight reduction and performance enhancement. As important as the weight reduction and high strength that high kink rigid rod-like polyarylenes, such as PrimoSpire® PR-250, can provide in aircraft fasteners, essentially non-electrically conductive materials Use also provides advantages. The electrical properties of PrimoSpire® PR-250 and 30% carbon fiber PEEK are shown in Table 5.

By avoiding dissimilar metal connections, galvanic corrosion is prevented. Because corrosion can occur even with similar metals, the use of non-conductive fasteners provides additional protection from corrosion. This often results in reduced maintenance costs and reduced downtime. The thermoplastic molded fastener will never corrode and will not participate in any galvanic corrosion of other parts. The flammability, fuming, and toxicity data for the PrimoSpire® PR-250 material is shown in Table 6. As suggested by the data, the materials are inherently flame retardant (without the use of additives), generate little smoke and are non-toxic, both of which are desirable properties for aircraft applications. is there.

Set 2
For purposes of illustration, photographs showing various fasteners made of the latest generation high kink rigid rod polyarylene PrimoSpire® PR-250 polyphenylene are shown in FIG.

  In the event that any disclosure of patents, patent applications, and publications incorporated herein by reference conflicts with this specification to the extent that the term is unclear, this specification shall control.

Claims (11)

A polymeric material comprising at least one kink-shaped rigid rod-like polyarylene (P), wherein the repeating unit is a repeating unit (R) of one or more formulas consisting of optionally substituted arylene groups ( A fastener (F) consisting of M), wherein the optionally substituted arylene group is substituted by each of its two ends by two other cases via a direct C-C bond Bonded to an arylene group which may be substituted, said repeating unit (R)
-0 to 75 mol% based on the total number of moles of the repeating unit (R),
A rigid rod-forming arylene unit (Ra) selected from p-phenylene optionally substituted by at least one monovalent substituent ;
-25 to 100 mol%, based on the total number of moles of the repeating unit (R),
(I) m-phenylene optionally substituted by at least one monovalent substituent or (ii) both m-phenylene and o-phenylene, independently of one another, at least one monovalent substituent. A kink-forming arylene unit (Rb) composed of optionally substituted m-phenylene and o-phenylene ;
A fastener, subject to   Fastener according to claim 1, characterized in that the number of moles of the kink-forming arylene units (Rb) is at least 40%, based on the total number of moles of the repeating units (R).   Fastener according to claim 1 or 2, characterized in that the number of moles of the kink-forming arylene units (Rb) is at most 65% based on the total number of moles of the repeating units (R). . The rigid rod-forming arylene unit (Ra) is p-phenylene substituted with a phenylketone group, and the kink-forming arylene unit (Rb) is unsubstituted m-phenylene. The fastener of any one of 1-3 . The fastener according to any one of claims 1 to 4 , wherein the fastener is a threaded fastener. Fastener according to claim 5 , characterized in that all screw parts are composed of the polymer material (M) and the surface of the screw part occupies more than 20% of the total surface of the fastener. 7. Fastener according to claim 5 or 6 , characterized in that it is selected from the group consisting of bolts, nuts, screws, headless screws, scribets, threaded studs, and threaded bushings. The fastener according to any one of claims 1 to 4 , wherein the fastener is a screwless fastener. 9. Fastener according to claim 8 , characterized in that it is selected from the group consisting of pins, retaining rings, rivets and fastening washers. At least one fastener including (F), self-propelled transport according to any one of claims 1-9. 11. A self-propelled transport according to claim 10 , characterized in that it is an aircraft.

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